Preparation of inorganic acid esters of higher glycols



acids, in particular sulphuric acid. and, undercertaineircumstamsuhsequenthydrolysiswith; diluted acids. and the like.The satu-- Patented Sept. I

UNITED STATES- PREPARATION or 'mon'cmo ACID i su'ims V. or manna GLYCOLSI Walther Schranth, Berlin-Dahlem, and Richard Hueter, Bosslau inAnhalt, Germany, assignors,

by mesne assignments,

to "Unieliem" Chemikalien Handeis A.-G., Zurich, Switieriand, acorporation of Switzerland No Drawing. Application-May a,1932,8erlal-No. 1 609,035. In Germany May 4, 19:1

10 Claims. (01. zoo-99.12)

Oflate, it was repeatedly proposed to produce.

agents employed in the manufacture of textiles by sulphonating primaryalcohols of high molecular weight, the constitution of which correspondsto normal fatty acids.

These known products could be introduced foremostly only for use intextile improving processes,

as they are either diiiicultly soluble-especially allwl sulphuric acidcompounds of high molecular weight--or 'may only be obtained in adequatepurity .by processes involving considerable technical difficulties. Inaddition, their resisting powers against the effects of acids,furthermore the solubility of the lime and magnesia salts are mostly notgreat enough for all purposes of application. i I r It was now foundthat the acid esters of alkylene glycols of high molecular weight andpolybasic acids, containing one or more acid groups, as well as theirsalts do not the aforestated shortcomings, and in addition representagents for wetting, levelling, dispersing, and washing with surprisinglyadvantageous effects. Furthermore, they give textile goods 9. soft,flexible feel, and owing to their lime and magnesia salts being easilysoluble, they may be used without hesitation in hardwater, and inconsequence of their stability against acids also in acid washingliquors and the like. Clear aqueous solutions are ob-.

tained with solvents of alcoholic nature, hydrogenated phenols, as wellas chlorinated hydrocarbons, and homogeneous dispersions are obtainedwith other-substances insoluble in water, fats, waxes, fatty acids andthe like. also not salted out by concentrated salt solutions.

Alkylene glycols, as described above, are aqueous additive compounds ofthe unsaturated alcooil, essentially of octadecen (9) -ol-'(1), somehexadecen (8) -ol-(1) and inconsiderable'quantities of the correspondingwith 20 carbon atoms. These a are'saturatedbytreatmentwithratedsubstancesbelnngtothesroupofalkylene They are glycols, and containone terminal hydroxyl group v and a further one at one of the centralcarbon atoms. Any quantities of these polyvalent alcohols maybe easilyproduced from raw materials,

for which only limited technical use existed till 5 now. The conversionof alcohols into esters of poiybasic acids is performed in the knownmanner, for instance by treating with sulphuric acid or othersulphonatingagents. Acid phosphoric acid esters, esters of polybasicorganic acids, especially of sulfocarbomlic acids and the like actsimilar to derivatives of sulphuric acid. But.

sulphuric acid esters are most easily accessible.

Example 1 I 83-90) principally hexadecenyland octadecenylalcohols asseparated from the solid ingredients are reacted with sulfuric acid at atemperature reacted with chloro-sulfonic acid, a product is -i obtainedwhich is especially suitable for treatment of raw, grea'sy'wool. Thereactions so far as they 25 can be represented by formula are believedoccur substantially asfollows:

car-(clhirflwnqclmronron pins hydration Q by means of sull'onatingcm-(orhx-omn-wmx-cm-on H a J V cm-(cmy-om-cn-mEhm-o-som Whether ornotthe formulas I represent the reactions the products resulting areparticularly effective for the treatment of fibrous 4 material. Afterneutralization with'sodalye theproductisuiruuivediusoo-iooorimrsthequuutitr ofw'ater. Ifgreasywoolistreatedfgir 15 minutes still-50 withthis solutioncleanidesreased wool. V

is obtained whichis-ready for manufachlm,

am le:

is If fatty alcohols of sperm-oil (iodine number or! 1 laundries onlyhaving extremely hard water at their disposal. It is expedient to adjustthe neutralized sulphonate-to the consistency of soft soap by addingwater. The application is the same as of common soap, but all lossesofmaterial due to precipitation of lime and are eliminated, besidesdamages to the, linen on account of deposits of these products on theflbres are avoided. The sulphonate may alsobe em.- ployed in combinationwith common additions to soap as well as mixed'with soap itself; In thelatter case, too, the stability against substances which harden thewater is maintained to a high degree; as the sulphonate dispersesdeposits oflime-soap. a

samp e 3 -A levelling agent, of which an addition of 0.2%

to acid dyeing baths afl'ords levelling eifects particularly with hanksof wool and textiles and favorably. influences the feel of the goods, isob tained. by sulphonating hydrated, unsaturated. fatty alcohols ofsperm-oil, which..are free of solid components. Such addition agents:re-

sisting the 0.5% contents of free sulphuric acidin the dyeing bath areparticularly obtained if the raw hydration-mix'tiu-e is freed byfractional distillation of the first runnings boiling under 220 at '18mm. mercury pressure and sulphonating with a quantity of chlorosulphonicacid corresponding to the acetyl saponiiication number. Theproduct'iinislied in the usual manner, is concentrated byvaporization tothe consistency of soft soap.

Weclaimz- 1. The method of producing alhl sulfates which comprisesproducing'an alkvl glycol mixture from sperm oil and reacting the samewith chlorosulfonic acid in the proportion necessary to replace bothhydroxyl-groups as indicated by the .acetyl number.

2. The method of producing alkyl sulfates which comprises producinganalkylglycol. mix

true from sperm oil, said glycols containing essentially 16 to 18 carbonatoms in the molecule and reacting the same with chlorosulfonic acid.

in the proportion necessary to replace both hydroxyl groups as indicatedby the acetyl number.

3. The method of producing alkyl sulphates which comprises producing analkyl glycol. mixtureirom sperm oil, said glycols containing essentially18to'18carbonatogmsinthe molecule,' reacting the same withchloro-sulfonic acid inthe proportion to replace both hydronl groups asindicated by the acetyl number, and

neutralizing with an alkali metal acid esters" .soformed.

-mm. mercury pressure and reacting the remain-- ..to produce sulfuricacid esters thereof.

4. The method of producing alkyi sulfates which comprises, reactingunsaturated alcohols derived from -sperm oil with concentratedsulfuric'acid at temperatures below 5 C. .to'produce sulfuric acidesters subjecting the reaction 5 products tothe action of boiling waterto produce dihydroxy alcohols from said esters removing/the water andreacting the alcohols with chlorosulfonic -acid to produce sulfuric acidesters.

5. The method of -producing alkyl sulfates.

. which comprises reacting-unsaturated alcohols derived from sperm oilwith concentrated sulfuric acid at temperatures below 5 C. to producesulfuric acid esters subjecting the reactionlti products to the actionof boiling water to pro-,.

duce dihydroiw alcohols from said esters,--removing the water,separating by fractional distillation the fraction boiling below 220 C.at 18 20 der with a quantity of chlorosulfonic acid necessary to replacethe.hydroxyl group as-indicate by. the acetyl number. W

1 6. The method of producing substances suitable a wetting, levelling,dispersin orcleaning 25 agents which comprises reacting a. polybasicacid "selected from the group consisting of sulfuric acid,chlorosulfonic acid, phosphoric acids and sulforcarboxylic acid withanalkyl glycol of higher molecular weight obtained fromsperm oil,thereby forming acid esters.

7. The method of producing substances suit- :able as wetting, levelling,dispersing .or cleaning agents which comprises esterifying a highermolecular dihydroxyalcohol of primary and secondary structure with aphosphoric acid.

8. The method of producing substances suitable as wetting, levelling,dispersing or cleaning agents which comprises esterifying -a higher ableas wetting, levelling, dispersing or cleaning agents which comprisestreating unsaturated alcohols obtained from sperm oil with sulfuric acidthereby saturating the alcohols, hydrolyzing to produce alkyl glycols,sulfating'said glycols v w 7 WALTHER SCHRAUTH,

